Regio- and chemoselective magnesiation of protected uracils and thiouracils using TMPMgCl·LiCl and TMP2Mg·2LiCl

Abstract

Two successive regio- and chemoselective magnesiations using TMPMgCl x LiCl and TMP(2)Mg x 2 LiCl enable the full functionalization of protected uracils and thiouracils in good to excellent yields.

Regio‐ und chemoselektive Metallierung von Arenen und Heteroarenen mit gehinderten Metallamidbasen

“…[196] Die Verwendung einer dirigierenden Gruppe, wie einer Phosphordiamidatfunktion, erweist sich ebenfalls als nützlich für die Funktionalisierung von Chinoxalinen. So wurde das [178] Funktionalisierte nichtaromatische Substrate werden ebenfalls mit TMP 2 Mg·2 LiCl (3) magnesiert. Das Enolphosphat 257 mit Campher-Gerüst wird durch 3 (25 8C, 30 min) in das Magnesiumderivat 258 umgewandelt.…”

TMP-cadmiate: A Base for Efficient and Chemoselective Deprotonative Metallation Reactions of Aromatic Compounds

“…TMPMgCl·LiCl at room temperature [67]. The (TMP) 3 CdLi-promoted reaction took place in a satisfying yield using the Cd-Li base, but with a complete lack of regioselectivity, leading to the 5-and 6-iodo derivatives 42b1 and 42b2 in a 43:57 ratio and 84% overall yield (entry 2).…”

Unusual Regioselective Reactions of 2,4-Bis(methylsulfanyl)pyrimidine under Modified Suzuki and Stille Cross-Coupling Conditions

“…When the reactions were performed at the reflux temperature using 2.5 equivalents of the organometallic reagents, reasonable yields of the disubstituted coupled products 4a-e were obtained (Table 1, entries [11][12][13][14][15][16][17][18][19][20]. When CuMeSal was used as cofactor, 4a-c were obtained in 69-71% yields from the Suzuki reaction (entries 11, 13, and 15) and slightly higher yields (74-79%) of 4d and 4e were obtained from the Stille coupling (entries 17 and 19).…”